Science China Materials

, Volume 60, Issue 11, pp 1109–1120 | Cite as

Octahedral PtNi nanoparticles with controlled surface structure and composition for oxygen reduction reaction

  • Yizhong Lu (逯一中)
  • Larissa Thia
  • Adrian Fisher
  • Chi-Young Jung
  • Sung Chul Yi
  • Xin Wang (王昕)


Controlling the surface structure and composition at the atomic level is an effective way to tune the catalytic properties of bimetallic catalysts. Herein, we demonstrate a generalized strategy to synthesize highly monodisperse, surfactant-free octahedral Pt x Ni1−x nanoparticles with tunable surface structure and composition. With increasing the Ni content in the bulk composition, the degree of concaveness of the octahedral Pt x Ni1−x nanoparticles increases. We systematically studied the correlation between their surface structure/composition and their observed oxygen reduction activity. Electrochemical studies have shown that all the octahedral Pt x Ni1−x nanoparticles exhibit enhanced oxygen reduction activity relative to the state-of-the-art commercial Pt/C catalyst. More importantly, we find that the surface structure and composition of the octahedral Pt x Ni1−x nanoparticles have significant effect on their oxygen reduction activity. Among the studied Pt x Ni1−x nanoparticles, the octahedral Pt1Ni1 nanoparticles with slight concaveness in its (111) facet show the highest activity. At 0.90 V vs. RHE, the Pt mass and specific activity of the octahedral Pt1Ni1 nanoparticles are 7.0 and 7.5-fold higher than that of commercial Pt/C catalyst, respectively. The present work not only provides a generalized strategy to synthesize highly monodisperse, surfactant-free octahedral Pt x Ni1−x nanoparticles with tunable surface structure and composition, but also provides insights to the structure-activity correlation.


PtNi octahedral concave surface structure oxygen reduction reaction 



双金属催化材料的催化性质可以通过在原子水平下控制材料的表面结构和组成进行有效调节. 本文发展了一种普适性的方法合成 具有高度分散性、洁净表面和可调的表面结构和组成的Pt x Ni1−x八面体纳米粒子. 研究发现在反应过程中, 通过增加Ni前驱体的含量, 合成 的Pt x Ni1−x八面体纳米粒子的(111)晶面的凹陷程度逐渐加大. 我们系统研究了Pt x Ni1−x八面体纳米粒子的表面结构或组成与其氧还原电催化 活性之间的相互关系. 电化学研究结果表明所有的Pt x Ni1−x八面体纳米粒子均表现出比标准商业Pt/C催化剂更高的氧还原活性. 更重要的 是, 我们发现Pt x Ni1−x八面体纳米粒子的表面结构和组成对其氧还原电催化活性具有很大的影响. 研究发现, 具有轻微(111)晶面凹陷程度的 Pt1Ni1八面体纳米粒子显示出最高的氧还原电催化活性. 在0.9 V(相对于标准氢电极)电势条件下, Pt1Ni1八面体纳米粒子的氧还原质量活性 和面积活性分别为标准商业Pt/C催化剂的7.0和7.5倍. 该研究不仅提供了一种普适性的方法合成具有高度分散性、洁净表面和可调的表面 结构和组成的Pt x Ni1−x八面体纳米粒子, 同时可为理解催化材料的结构-性质相互关系规律提供指导.



This research was supported by the National Research Foundation, PrimeMinister’s Office, Singapore under its CREATE Programme. We also acknowledge financial support by the Defence Acquisition Program Administration and Agency for Defence Development (UD120080GD), Republic of Korea.

Supplementary material

40843_2017_9029_MOESM1_ESM.pdf (4.9 mb)
Octahedral PtNi nanoparticles with controlled surface structure and composition for oxygen reduction reaction


  1. 1.
    Stamenkovic VR, Fowler B, Mun BS, et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science, 2007, 315: 493–497CrossRefGoogle Scholar
  2. 2.
    Huang X, Zhao Z, Cao L, et al. High-performance transitionmetaldoped Pt3Ni octahedra for oxygen reduction reaction. Science, 2015, 348: 1230–1234CrossRefGoogle Scholar
  3. 3.
    Choi SI, Xie S, Shao M, et al. Synthesis and characterization of 9 nm Pt–Ni octahedra with a record high activity of 3.3 A/mgPt for the oxygen reduction reaction. Nano Lett, 2013, 13: 3420–3425CrossRefGoogle Scholar
  4. 4.
    Zhang J, Yang H, Fang J, et al. Synthesis and oxygen reduction activity of shape-controlled Pt3Ni nanopolyhedra. Nano Lett, 2010, 10: 638–644CrossRefGoogle Scholar
  5. 5.
    Huang X, Zhao Z, Chen Y, et al. A rational design of carbon-supported dispersive Pt-based octahedra as efficient oxygen reduction reaction catalysts. Energ Environ Sci, 2014, 7: 2957–2962CrossRefGoogle Scholar
  6. 6.
    Carpenter MK, Moylan TE, Kukreja RS, et al. Solvothermal synthesis of platinum alloy nanoparticles for oxygen reduction electrocatalysis. J Am Chem Soc, 2012, 134: 8535–8542CrossRefGoogle Scholar
  7. 7.
    Cui C, Gan L, Li HH, et al. Octahedral PtNi nanoparticle catalysts: exceptional oxygen reduction activity by tuning the alloy particle surface composition. Nano Lett, 2012, 12: 5885–5889CrossRefGoogle Scholar
  8. 8.
    Cui C, Gan L, Heggen M, et al. Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. Nat Mater, 2013, 12: 765–771CrossRefGoogle Scholar
  9. 9.
    Kodama K, Jinnouchi R, Takahashi N, et al. Activities and stabilities of Au-modified stepped-Pt single-crystal electrodes as model cathode catalysts in polymer electrolyte fuel cells. J Am Chem Soc, 2016, 138: 4194–4200CrossRefGoogle Scholar
  10. 10.
    Jinnouchi R, Toyoda E, Hatanaka T, et al. First principles calculations on site-dependent dissolution potentials of supported and unsupported pt particles. J Phys Chem C, 2010, 114: 17557–17568CrossRefGoogle Scholar
  11. 11.
    Tian N, Zhou ZY, Sun SG, et al. Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science, 2007, 316: 732–735CrossRefGoogle Scholar
  12. 12.
    Wang D, Xin HL, Hovden R, et al. Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat Mater, 2012, 12: 81–87CrossRefGoogle Scholar
  13. 13.
    Xia BY, Wu HB, Wang X, et al. One-pot synthesis of cubic PtCu3 nanocages with enhanced electrocatalytic activity for themethanol oxidation reaction. J Am Chem Soc, 2012, 134: 13934–13937CrossRefGoogle Scholar
  14. 14.
    Xia BY, Wu HB, Li N, et al. One-pot synthesis of Pt-Co alloy nanowire assemblies with tunable composition and enhanced electrocatalytic properties. Angew Chem Int Ed, 2015, 54: 3797–3801CrossRefGoogle Scholar
  15. 15.
    Stamenkovic VR, Mun BS, Arenz M, et al. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat Mater, 2007, 6: 241–247CrossRefGoogle Scholar
  16. 16.
    van der Vliet DF, Wang C, Tripkovic D, et al. Mesostructured thin films as electrocatalysts with tunable composition and surfacemorphology. Nat Mater, 2012, 11: 1051–1058CrossRefGoogle Scholar
  17. 17.
    Gasteiger HA, Kocha SS, Sompalli B, et al. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl Catal B-Environ, 2005, 56: 9–35CrossRefGoogle Scholar
  18. 18.
    Lu Y, Jiang Y, Gao X, et al. Strongly coupled Pd nanotetrahedron/ tungsten oxide nanosheet hybrids with enhanced catalytic activity and stability as oxygen reduction electrocatalysts. J Am Chem Soc, 2014, 136: 11687–11697CrossRefGoogle Scholar
  19. 19.
    Gan L, Cui C, Heggen M, et al. Element-specific anisotropic growth of shaped platinum alloy nanocrystals. Science, 2014, 346: 1502–1506CrossRefGoogle Scholar
  20. 20.
    Gan L, Heggen M, Cui C, et al. Thermal facet healing of concave octahedral Pt–Ni nanoparticles imaged in situ at the atomic scale: implications for the rational synthesis of durable high-performance ORR electrocatalysts. ACS Catal, 2016, 6: 692–695CrossRefGoogle Scholar
  21. 21.
    Jin M, Zhang H, Xie Z, et al. Palladium nanocrystals enclosed by {100} and {111} facets in controlled proportions and their catalytic activities for formic acid oxidation. Energ Environ Sci, 2012, 5: 6352–6357CrossRefGoogle Scholar
  22. 22.
    Chen C, Kang Y, Huo Z, et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science, 2014, 343: 1339–1343CrossRefGoogle Scholar
  23. 23.
    AránAis RM, Dionigi F, Merzdorf T, et al. Elemental anisotropic growth and atomic-scale structure of shape-controlled octahedral Pt–Ni–Co alloy nanocatalysts. Nano Lett, 2015, 15: 7473–7480CrossRefGoogle Scholar
  24. 24.
    Wu Y, Cai S, Wang D, et al. Syntheses of water-soluble octahedral, truncated octahedral, and cubic Pt–Ni nanocrystals and their structure–activity study in model hydrogenation reactions. J Am Chem Soc, 2012, 134: 8975–8981CrossRefGoogle Scholar
  25. 25.
    Snyder J, McCue I, Livi K, et al. Structure/processing/properties relationships in nanoporous nanoparticles as applied to catalysis of the cathodic oxygen reduction reaction. J Am Chem Soc, 2012, 134: 8633–8645CrossRefGoogle Scholar
  26. 26.
    Garsany Y, Baturina OA, Swider-Lyons KE, et al. Experimental methods for quantifying the activity of platinum electrocatalysts for the oxygen reduction reaction. Anal Chem, 2010, 82: 6321–6328CrossRefGoogle Scholar
  27. 27.
    Lu Y, Jiang Y, ChenW. PtPd porous nanorods with enhanced electrocatalytic activity and durability for oxygen reduction reaction. Nano Energ, 2013, 2: 836–844CrossRefGoogle Scholar
  28. 28.
    Shao M, Chang Q, Dodelet JP, et al. Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev, 2016, 116: 3594–3657CrossRefGoogle Scholar
  29. 29.
    Markovic NM, Schmidt TJ, StamenkovicV, et al. Oxygen reduction reaction on Pt and Pt bimetallic surfaces: a selective review. Fuel Cells, 2001, 1: 105–116CrossRefGoogle Scholar
  30. 30.
    Guo S, Zhang S, Sun S. Tuning nanoparticle catalysis for the oxygen reduction reaction. Angew Chem Int Ed, 2013, 52: 8526–8544CrossRefGoogle Scholar
  31. 31.
    Sun S, Zhang G, Geng D, et al. A highly durable platinum nanocatalyst for proton exchangemembrane fuel cells: multiarmed starlike nanowire single crystal. Angew Chem Int Ed, 2011, 50: 422–426CrossRefGoogle Scholar
  32. 32.
    Wang C, Chi M, Wang G, et al. Correlation between surface chemistry and electrocatalytic properties of monodisperse PtxNi1-x nanoparticles. Adv Funct Mater, 2011, 21: 147–152CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Yizhong Lu (逯一中)
    • 1
    • 2
  • Larissa Thia
    • 1
  • Adrian Fisher
    • 3
  • Chi-Young Jung
    • 4
  • Sung Chul Yi
    • 5
  • Xin Wang (王昕)
    • 1
  1. 1.School of Chemical and Biomedical EngineeringNanyang Technological UniversitySingaporeSingapore
  2. 2.Cambridge Centre of Advanced Research in Energy Efficiency in Singapore (CARES)SingaporeSingapore
  3. 3.Department of Chemical Engineering and BiotechnologyUniversity of CambridgeCambridgeUK
  4. 4.Hydrogen and Fuel centerKorea Institute of Energy Research (KIER)Jellabuk-doRepublic of Korea
  5. 5.Department of Chemical EngineeringHanyang UniversitySeoulRepublic of Korea

Personalised recommendations